Anthraquinone derivatives and process of making same



Patented Mar. 26, 1935 UNITED STATES.

PATENT OFFICE AN THRAQUINONE DERIVATIVE S AND PROCESS OF MAKING SABIE Basel, Switzerland No Drawing. Original application May 31, 1932,

Serial No. 614,610.

Divided and this application March 30, 1933, Serial No. 663,656. In

Switzerland June 29,

' 10 Claims.

This application is a division of our application for patent Serial No. 614,610 filed in the United States of America on May 31', 1932, and in Switzerland on June 29, 1931, of which the following is a full, clear, and exact specification.

This invention relates to the manufacture of new anthraquinone derivatives and their application as dyestuffs. It comprises the process of making these derivatives as well as the derivatives themselves. 7

The invention is based on the observation that in 1 acylamino 3 halogen-anthraqumones, obtainable for example by acylating l-amino-3-halogen-anthraquinones, the halogen may be exchanged in a surprisingly smooth manner, with elimination of hydrogen'halide or a salt thereof, for the most various residues.

The reaction is carried out by causing compounds containing at least one replaceable atom of hydrogen or a metal attached to nitrogen, oxygen or sulfur to react on 1-acylamino-3-halogen-anthraqu'inones.

Among the 1-acylamino-3-halogen-anthraquinones which may be used in the present process the following may for example be nentioned 1 formylamino 3 bromanthraquinone, 1acetylamino-3-bromanthraquinone, l-benzoylamino-3-bromanthraquinone, 1 (4' -chloro) benzoylamino 3 chloranthraquinone, 1 naph thoylamino-3-chloranthraquinone, 1- (2-ethoxy-) naphthoylamino 3 bromanthraquinone, 1 benzene sulfamino -3- bromanthraquinone, 1 -naphthalenesulf amino -3 chloranthraquinone, 1 1 anthraquinonecarbonyl amino 3 chloranthraquinona, 1- (2'-anthraquinor ecarbonyl-) amino- 3-bromanthranquinone.

Compounds containing at least one replaceable atom of hydrogen or a metal attached to nitrogen, oxygen or sulfur, and which may be converted with the 1-acylamino-3-halogen-anthraquinones are for example the following:alcoholates, phenolates, xanthates, mercaptans, thicphenols, thionaphthols, sulfamides, ammonia, primary and secondary amines of the aliphatic or aromatic series, such as methylamine, glycocoll, aniline, toluidine, phenylenediamine, naphthylamine, or the highly condensed ring systems, such as aminoanthraquinones, aminopyranthrones, aminoanthanthrones, aminodibenzanthrones.

The reaction of the l-acylamino-3-halogenanthraquinones with the compounds just named is preferably carried out in a diluent of high boiling point in presence of agents that bind acids, such as anhydrous sodium acetate, potassium acetate, calcined alkali carbonates, copper oxide, magnesium oxide, and of catalysts, such as metallic copper and its compounds. The yields are generally approximately quantitative, and the products of the reaction are almost always obtained in crystalline form.

The products obtained in this manner may already themselves be valuable dyestuffs, but they may also be used as intermediate products for making further dyestuffs.

These latter are obtained by treating with condensing agents those products which are obtained by the reaction of compounds containing at least one replaceable atom of hydrogen or a metal attached to nitrogen, oxygen or sulfur with l-acylamino -3- halogen anthraquinones. Particularly valuable dyestuiis are obtained in the treatment with condensing agents, probably under carbazolation, from those products which are obtainable by reacting with the cited highly condensed ring systems on 1-acylamino-3-halogen-anthraquinones.

As condensing agents there may for example be mentioned concentrated sulfuric acid, chlorsulfonic acid, fiuor-sulfonic acid, aluminium chloride as such, or mixed with alkali halides, or in presence of organic bases, or as an ammonia double compound.

The new anthraquinone derivatives obtainable according to the present process yield in dyeing valuable tints of very good fastness properties. For dyeing they can also be used in the form of their leuco-compounds, for instance their leuco-esters.

The following examples illustrate the invention, the parts being by weight:-

Example 1 12 parts of 1-benzoylamino-3-bromanthraquinone, 8 parts of l-aminoanthraquinone, 8 parts of potassium acetate, 1 part of copper acetate and 200 parts of nitrobenzene are heated together to boiling for ,6 hours while stirring. The whole is filtered at 50 C. and the solid matter is washed with nitrobenzene, then with alcohol and finally with hot water. There are obtained 11 parts of a red crystalline powder. This product of the probable formula dissolves to a pure blue solution in concentrated sulfuric acid or chlorsulfonic acid. When precipitated from concentrated sulfuric acid solution thedyestuif dyes cotton in a cold or warm vat a strong brick red of very good properties fastness.

of dyes cotton in the vat very vivid and strong orange tints which exhibit very good properties Example 2 of fastness.

10 parts of 1-benzoylamino-3-bromanthra- Example 4 quinone, 9 parts of lz5-monobenzoyldiamino- 1 pa f yl m -3- r0m h q nanthraquinone, parts of anhydrous di one, 2.4 parts of 1:5-diaminoanthraquinone, 5 acetate, 1 part of copper acetate and 150 parts of parts O a yd Sodium a 1 P t Of D- nitrobenzene are heated together to boiling for p acetate and 150 Parts Of hitwbenzene are 2 6 hours and the mass is worked up as described gethel heated t o n or 6 urs as desc ibed in Example 1. There are obtained well formed in Exemple The new compound of the p small red needles in a yield of more than 90 per able formula cent. of that indicated by theory. By precipitating the dyestufi of the probable formula 0 O 0 Nil-COO II I 0 0 NH O 0 l O\/ I 0 from sulfuric acid of 93 per cent. strength at a temperature below 5 C. there is obtained a red paste. This compound dyes cotton in a cold or COHN o is isolated by filtration at about 50 C. It is a red warm hydrosulfite vat strong brownish red tints crystalline p which after precipitation from of good properties of fastness concentrated sulfuric acid solution dyes cotton in When 1:8-monobenzoyldiaminoanthraquinone the Vat Strong bordeaux tints 0f y good P p is used instead of the 1:5-compound a similar ties of fastnessdyestuff of the probable formula Example 5 A mixture of parts of l-benzoylamino-3- bromanthraquinone, 10 parts of 1: 4-monobenzoyldiaminoanthraquinone, 5 parts of potassium acetate, 1 part of copper acetate and 200 parts of Nil-GOO nitrobenzene is converted as described in Example NEE 1, into the corresponding anthrirnide of the prob- I able formula of very good properties or fastness is obtained.

Example 3 5 parts of the compound obtainable as described in the first paragraph of Example 2 are introduced at 0-5 C. into 50 parts of chlorosultonic acid and the whole is then stirred for 1 hour at 30-35 C. The pure blue solution becomes I H dirty brown after a few minutes and then grad- GOHN o ually reddish blue. It is now diluted at 0-5 C. W 50 Parts Of Sulfuric acid f 80 per cent. when this is treated with acid condensing agents, strength and the mass is poured upon ice and such as chlorosulfonic acid or sulfuric acid, at then filtered. The neutral press cake is treated ordinary temperature for a short time there is with dilute sodium hypochlorite solution for 2% obtained by dilution with water, filtration and hours at '70-'75 C. After filtering and drying the drying, a brown powder of the probable formula solid matter of the probable formula 0 NH-OOO there is produced ashining red powder which which dyes cotton in a cold or warm vat very strong brown tints exhibiting good properties of fastness.

Example 6 1 gram of the dyestufi made as described in Example 3, 5 cc. of caustic soda solution of 36 B. and 100 cc. of water at 2530 C. are made into a paste, 2 grams of hydrosulfite conc. powder are added and vatting is continued for hour at the above temperature. To this dye-bath there are added 3 cc. of caustic soda solution of 36 B. and 1 gram of hydrosulfite and the whole is made up, including the stock vat, to 2 litres and the stock vat is added. The goods are entered at 25-30 C. and handled for 4 hour. There are then added 20 grams of sodium chloride or calcined sodium sulfate and dyeing is continued for 1 hour at 25-30 C. After winding off, the goods are oxidized for hour in the air, rinsed, scoured, rinsed and soaped at the boil. Orange tints are obtained.

Example 7 40 parts of aluminium chloride are slowly'introduced into 40 parts of pyridine so that the temperature does not rise above 100 C. To this mixture 10 parts of the condensation product obtained as described in Example 1 from l-benzoylamino-3-bromanthraquinone and l-aminoanthraquinone are then added, and the whole is heated for 1 hour in a reflux apparatus. The fusion mass, while still hot, is then poured into an alkaline aqueous hydrosulfite solution of about 40 C. and stirred for a short time. A brown solution is thus obtained from which the dyestuff of the probable formula NHO may be separated byvigorous stirring in the air, if necessary after preliminary filtration. By treatment with an aqueous sodium hypochlorite solution the dyestuff is obtained in a somewhat purer state yet. When dry it is a brown powder. In concentrated sulfuric acid it dissolves to a red solution. Cotton is dyed from a cold and a warm vat very strong and fast yellow-brown tints.

What we claim is:-

l. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing 1-acy1amino-3- halogen-anthraquinones with amines of the anthraquinone series to react with agents having a condensing action.

2. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-acylamino-3-ha1ogen-anthraquinones with amines of the anthraquinone series to react with acid agents having a condensing action.

3. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-acylamino-3-bromanthraquinones with amines of the anthraquinone series to react with acid agents having a condensing action.

4. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-benzoylamino-3-bromanthraquinones with amines of the anthraquinone series to react with acid agents having a condensing action.

5. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-benzoylamino-3-bromanthraquinones with aminoanthraquinones to react with acid agents having a condensing action.

6. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-ben-- zoylamino-3-bromanthraquinones with aminoanthraquinones to react with sulfuric acids in which one hydroxyl group may be replaced by halogen.

'7. Process for the manufacture of anthraquinone derivatives consisting in causing the products which are obtained by condensing l-benzoylamino-3-bromanthraquinones with arninoanthraquinones to react with chlorosulfonic acid.

8. Process for the manufacture of an anthraquinone derivative consisting in causing the product which is obtained by condensing l-benzoylamino-S-bromanthraquinone with l-amino-- benzoylaminoanthraquinone to react with chlo-V rosulfonic acid.

9. Anthraquinone derivatives of the general formula! NHC1 Y in which the two carbon atoms C1 and C2 belong to an anthraquinone nucleus wherein C1 stands in a-position and C2 in ,B-position, which products form orange to red powders which dissolve in concentrated sulfuric acid to red to blue solutions and dye cotton from the vat red to black tints of very good fastness properties.

10. Anthraquinone derivatives of the general formula 0 N H-benzoyl which products form orange powders which dissolve in concentrated sulfuric acid to brown solutions, and dye cotton from the vat orange tints of good fastness properties.

HERMANN HAUSER. MAX BOMMER. 

